{μ-6,6′-Dimeth­oxy-2,2-[propane-1,3-diylbis(nitrilo­methanylyl­idene)]diphenolato}trinitratocopper(II)dysprosium(III) methanol monosolvate

Lili Xu; Hong-Feng Li; Peng Chen; Peng-Fei Yan

doi:10.1107/S1600536811005253

. 2011 Feb 23;67(Pt 3):m367. doi: 10.1107/S1600536811005253

{μ-6,6′-Dimethoxy-2,2-[propane-1,3-diylbis(nitrilomethanylylidene)]diphenolato}trinitratocopper(II)dysprosium(III) methanol monosolvate

Lili Xu ^a, Hong-Feng Li ^a, Peng Chen ^a,^*, Peng-Fei Yan ^a

PMCID: PMC3051998 PMID: 21522291

Abstract

In the title heterodinuclear salen-type complex, [CuDy(C₁₉H₂₀N₂O₄)(NO₃)₃]·CH₃OH, the copper(II) ion is tetracoordinated by two imino N atoms [Cu—N = 1.961 (4) and 1.968 (4) Å] and two phenolate O atoms [Cu—O = 1.931 (3) and 1.938 (3) Å] in a planar geometry. The ten-coordinate Dy^III ion is ligated by six O atoms of three nitrate groups and four O atoms from the ligand [Dy—O = 2.368 (3)–2.601 (3) Å]. In the crystal, complex molecules and solvent molecules are linked by intermolecular O—H⋯O hydrogen bonds.

Related literature

For similar Cu–Ln complexes (Ln = lanthanide), see: Bao et al. (2010 ▶); Elmali & Elerman (2003 ▶, 2004 ▶); Wang et al. (2008 ▶); Xing et al. (2008 ▶). For bond-valence calculations, see: Pauling (1947 ▶).

Experimental

Crystal data

[CuDy(C₁₉H₂₀N₂O₄)(NO₃)₃]·CH₄O
M _r = 784.49
Triclinic,
a = 8.3572 (17) Å
b = 12.130 (2) Å
c = 13.891 (3) Å
α = 91.64 (3)°
β = 106.85 (3)°
γ = 99.52 (3)°
V = 1324.8 (4) Å³
Z = 2
Mo Kα radiation
μ = 3.68 mm⁻¹
T = 293 K
0.15 × 0.12 × 0.11 mm

Data collection

Bruker SMART1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.595, T _max = 0.667
13040 measured reflections
6008 independent reflections
5600 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.108
S = 1.05
6008 reflections
373 parameters
H-atom parameters constrained
Δρ_max = 2.37 e Å⁻³
Δρ_min = −0.88 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2003 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811005253/vm2074sup1.cif

e-67-0m367-sup1.cif^{(24.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811005253/vm2074Isup2.hkl

e-67-0m367-Isup2.hkl^{(294.1KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1M—H4M⋯O2ⁱ	0.89	2.03	2.852 (8)	152

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported financially by the National Natural Science Foundation of China (Nos. 20872030 and 20972043), Heilongjiang Province (Nos. 2009RFXXG201, GC09A402, GZ08A401and 2010td03) and Heilongjiang University.

supplementary crystallographic information

Comment

In continuation of the studies of salen-type lanthanide complexes (Elmali et al., 2003, Elmali et al., 2004), we present here the synthesis and the crystal structure of the title compound (Fig. 1). The Dy^III ion is ligated to six oxygen atoms from three bidentate nitrate groups and four oxygen atoms from the ligand, similar to what is found in previously published structures (Wang et al., 2008, Xing et al., 2008, Bao et al., 2010). The Dy—O bond distances are in the range of 2.368 (3) to 2.601 (3) Å, in accordance with the reported values. The planar coordinated Cu(II) ion is tetra-coordinated by two imino nitrogen atoms (Cu—N bond distance range, 1.961 (4)–1.968 (4) Å) and two phenolate oxygen atoms from the ligand (Cu—O bond distance range, 1.931 (3)–1.938 (3) Å). The positive charge of the Dy^III and Cu(II) ions are balanced by the ligand L^2- and three nitrate groups (L = N,N'- bis(2-oxy-3-methoxybenzylidene)-1,3-diaminopropane). However, bond valence calculations (Pauling, 1947) indicate a bond valency of +2 for the Dy ion. This difference is attributed to the longer bond distances of Dy—O. One MeOH molecule is dissociative in the complex, forming H-bonding with the adjacent nitrate group (O···O distance 2.852 (7) Å, Table 1). A methanol molecule is absent in the case of a reported Cu—Eu complex, where a similar coordination environment for Cu(II) and Eu(III) ions could be found (Xing et al., 2008). Furthermore, an acetone molecule is observed instead of the methanol molecule in the case of the reported structures with Sm(III) and Cu(II) ions in a similar coordination environment (Wang et al., 2008). Weak π-π interactions between adjacent aromatic rings of the 2-oxy-3-methoxybenzylidene groups could also be observed (Fig. 2, Cg(5)···Cg(5)ⁱdistance = 4.368 (3) Å, Cg(5) is the centroid of ring C5-C16, symmetry code (i): 1 - x, 1 - y, 1 - z).

Experimental

To a 1:1 MeOH/CH₂Cl₂ solution (20 ml) of H₂L (0.0684 g) and Cu(OAc)₂.2H₂O (0.0440 g) was added a MeOH solution (10 ml) of Dy(NO₃)₃].6H₂O (0.0753 g) at the ambient temperature. The color of the solution immediately changed to green. After stirring for 5 hrs, the solution was filtered to remove the suspended particles. Green single crystals suitable for X-ray determination were obtained by slow diffusion of diethylether into the filtrate in one week. [CuDy(C₁₉H₂₀N₂O₄)(NO₃)₃].CH₃OH Elemental Anal. Calc. for C₂₀H₂₄N₅O₁₄CuDy: C, 30.62; H, 3.08; N, 8.93 wt%, Found: C, 30.61; H, 3.10; N, 8.93 wt%.